CN107492654A - A kind of column lithium ion battery and its preparation technology - Google Patents
A kind of column lithium ion battery and its preparation technology Download PDFInfo
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- H01M4/00—Electrodes
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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Abstract
The invention belongs to a kind of column lithium ion battery and its preparation technology；Including box hat, lithium-ion electric core, it is respectively provided at insulating trip and lower insulating trip on lithium-ion electric core upper and lower part, positive plate, the first barrier film, negative plate and the second barrier film that lithium-ion electric core includes being sequentially stacked and winding, is provided with electrolyte inside box hat, positive plate includes aluminium foil and is located at the positive electrode active materials of aluminium foil surface；Negative plate includes copper foil and is located at the negative active core-shell material of copper foil surface；Electrolyte is nonaqueous electrolytic solution, and nonaqueous electrolytic solution includes nonaqueous solvents, lithium hexafluoro phosphate, double fluorine sulfonamide Asia lithium, difluoro-benzene and divinyl vinylene carbonates；With anode material for lithium-ion batteries structural stability it is good, the sintered density of solid-solution material and intensity can be improved, reduce roll-in in production when destruction to material crystal formation, reduce material capacity loss and improve cyclical stability the advantages of.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of column lithium ion battery and its preparation work
Skill.
Background technology
Lithium ion battery has output voltage height, discharging voltage balance higher than energy, the characteristics of having extended cycle life.So
Lithium ion battery has been widely used for notebook computer, digital camera, field of mobile phones.And more and more dynamic field,
Applied in energy storage field.Dynamic field and energy storage field are different from the single electrical appliance energy of digital domain in several watt-hours to several
Ten watt-hours, they generally require tens kilowatt hours, and even more high energy, separate unit cost is higher, therefore to the cycle life of battery
It it is also proposed higher and higher requirement.
Wherein anode material for lithium-ion batteries stratiform LiNi1/3Co1/3Mn1/3O2 is as a kind of new lithium ion battery
Positive electrode, its theoretical capacity reach 278mAh/g.LiNi1/3Co1/3Mn1/3O2 has an a-NaFeO2 type layer structures, Ni for+
Divalent, co are+trivalent, and Mn is+4 valencys, a small amount of Ni3+ and Mn3+.During charging, Mn4+ fixed prices, Ni2+ is changed into Ni4+, and Co3+ becomes
For Co4+.LiNi1/3Co1/3Mn1/3O2, has concentrated LiCoO2, tri- kinds of materials of LiNiO2, LiMnO2 each the advantages of, still
Because ternary material has Mn3+ influence in building-up process, Jahn-Teller effects are produced in charge and discharge process, cause manganese
Dissolving and electrolyte decomposition.So as to cause, battery capacity is too low, poor circulation.
The content of the invention
A kind of anode material for lithium-ion batteries structure is provided it is an object of the invention to overcome deficiency of the prior art
Stability is good, the sintered density of solid-solution material can be improved and intensity, destruction to material crystal formation when reducing roll-in in production,
Reduce material capacity loss and improve a kind of column lithium ion battery and its preparation technology of cyclical stability.
The object of the present invention is achieved like this：The column lithium ion battery includes box hat, lithium-ion electric core, set respectively
Insulating trip and lower insulating trip, lithium-ion electric core include the positive pole for being sequentially stacked and winding on lithium-ion electric core upper and lower part
Electrolyte is provided with inside piece, the first barrier film, negative plate and the second barrier film, box hat,
The positive plate includes aluminium foil and is located at the positive electrode active materials of aluminium foil surface；Described positive electrode active materials include
Following raw materials according is made according to parts by weight：Positive electrode 94-98 parts, vapor-grown carbon fibers 0.1-3 parts, Kynoar 1-3
Part and 1-METHYLPYRROLIDONE 10-40 parts；
The chemical formula of described positive electrode is：Li4Ni5-3XCo2XYXO8(0 ＜ X ＜ 0.5)；
The negative plate includes copper foil and is located at the negative active core-shell material of copper foil surface；Described negative active core-shell material includes
Following raw materials according is made according to parts by weight：95 parts of carbon negative pole material, 1 part of vapor-grown carbon fibers, sodium carboxymethylcellulose 1.5
50 parts of part, 2.5 parts of butadiene-styrene rubber and deionized water；Described carbon negative pole material is that Delanium, native graphite, mesocarbon are micro-
One of ball, petroleum coke, carbon fiber or thermal decomposed resins；
The electrolyte is nonaqueous electrolytic solution, and it is sub- that nonaqueous electrolytic solution includes nonaqueous solvents, lithium hexafluoro phosphate, double fluorine sulfonamide
Lithium, difluoro-benzene and divinyl vinylene carbonate；Nonaqueous solvents is by ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate
Form, ethylene carbonate, dimethyl carbonate, the volume ratio of methyl ethyl carbonate are 1: 5: 4；Contain 0.9mol/L in nonaqueous electrolytic solution
Lithium hexafluoro phosphate and the double fluorine sulfonamide Asia lithiums of 0.1mol/L, the percentage of the weight of difluoro-benzene and the weight sum of nonaqueous solvents
Than for 2%, the percentage of the weight of divinyl vinylene carbonate and the weight sum of nonaqueous solvents is 2%.
Preferably, described positive electrode active materials are made comprising following raw materials according according to parts by weight：96 parts of positive electrode, gas
30 parts of 2 parts of phase grown carbon fiber, 2 parts of Kynoar and 1-METHYLPYRROLIDONE；The chemical formula of described positive electrode is：
Li4Ni4.7Co0.2Y0.1O8；X=0.1.
A kind of preparation technology of column lithium ion battery, the preparation technology include the preparation method of positive plate, negative plate
Preparation method and electrolyte preparation method,
The preparation method of positive plate comprises the following steps：
Step 1：After nickel salt aqueous solution, cobalt saline solution, the yttrium salt aqueous solution are well mixed, mixed solution is made；
Step 2：Mixed solution described in step 1 is placed in reaction vessel, adds the mixing of ammoniacal liquor and highly basic
Liquid, reaction solution is set to carry out coprecipitation reaction；The pH value of described reaction solution is 11~12；
Step 3：Sediment after terminating to coprecipitation reaction in step 2 carries out washing and drying, the sediment after drying
Middle addition lithium salts mixed at high speed in ball mill；200~1000rpm of rotating speed of described mixed at high speed, ratio of grinding media to material 3: 1~10
: 1,8~30h of Ball-milling Time；
Step 4：Mixture in step 3 in ball mill after mixed at high speed was through high-temperature roasting 24 hours, after standing room temperature
Through pulverizing and sieving, positive electrode is made；The temperature of described high-temperature roasting is 800~1100 DEG C, the screen cloth to pulverize and sieve
For 100~400 mesh；
Step 5：By the positive electrode described in step 4, vapor-grown carbon fibers, Kynoar and N- methylpyrroles
Alkanone is placed on be uniformly dispersed in planetary high speed dispersing device after, be spread evenly across on aluminium foil, after roll-in be made positive plate；
The thickness of described aluminium foil is 12 μm, and described positive plate thickness is 130 μm；
The preparation method of negative plate：By carbon negative pole material, vapor-grown carbon fibers, sodium carboxymethylcellulose, butadiene-styrene rubber
It is respectively put into after being uniformly dispersed in planetary high-speed dispersion equipment, is spread evenly across on the copper foil that thickness is 6 μm with deionized water,
The negative plate that thickness is 130 μm is obtained after roll-in；
The preparation method of electrolyte comprises the following steps：
Step 1：Ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate are mixed, and are made non-aqueous after being well mixed
Agent；
Step 2：Lithium hexafluoro phosphate and double fluorine sulfonamide Asias lithium are added into the nonaqueous solvents described in step 1, is made
Lithium salts nonaqueous solvents；
Step 3：Difluoro-benzene is sequentially added into the lithium salts nonaqueous solvents described in step 2 and divinyl carbonic acid is sub-
Vinyl acetate, you can.
Preferably, described nickel salt aqueous solution is selected from nickel sulfate solution, nickel nitrate aqueous solution, nickel chloride aqueous solution or vinegar
One of sour nickel aqueous solution；Cobalt saline solution is selected from cobalt sulfate solution, cobalt nitrate aqueous solution, cobalt chloride solution or cobalt acetate water
One of solution；The yttrium salt aqueous solution be selected from the yttrium sulfate aqueous solution, yttrium nitrate aqueous solution, the yttrium chloride aqueous solution or the acetic acid yttrium aqueous solution it
One；The mol ratio of the cobalt in nickel, cobalt saline solution in nickel salt aqueous solution and the yttrium in the yttrium salt aqueous solution is 5-3x: 2x: x, institute
The X stated is more than 0, and less than 0.5.
Preferably, one kind in potassium hydroxide solution, sodium hydroxide solution, lithium hydroxide solution of described highly basic or
It is several.
The present invention is with anode material for lithium-ion batteries structural stability is good, can improve the sintered density of solid-solution material
The excellent of cyclical stability is lost and improves with the destruction in intensity, reduction production during roll-in to material crystal formation, reduction material capacity
Point.
Embodiment
The present invention is a kind of column lithium ion battery and its preparation technology, the column lithium ion battery include box hat,
Lithium-ion electric core, be respectively provided at insulating trip and lower insulating trip on lithium-ion electric core upper and lower part, lithium-ion electric core is included successively
Electrolyte is provided with inside the positive plate, the first barrier film, negative plate and the second barrier film that are stacked and wind, box hat,
The positive plate includes aluminium foil and is located at the positive electrode active materials of aluminium foil surface；Described positive electrode active materials include
Following raw materials according is made according to parts by weight：Positive electrode 94-98 parts, vapor-grown carbon fibers 0.1-3 parts, Kynoar 1-3
Part and 1-METHYLPYRROLIDONE 10-40 parts；
The chemical formula of described positive electrode is：Li4Ni5-3XCo2XYXO8(0 ＜ X ＜ 0.5)；
The negative plate includes copper foil and is located at the negative active core-shell material of copper foil surface；Described negative active core-shell material includes
Following raw materials according is made according to parts by weight：95 parts of carbon negative pole material, 1 part of vapor-grown carbon fibers, sodium carboxymethylcellulose 1.5
50 parts of part, 2.5 parts of butadiene-styrene rubber and deionized water；Described carbon negative pole material is that Delanium, native graphite, mesocarbon are micro-
One of ball, petroleum coke, carbon fiber or thermal decomposed resins；
The electrolyte is nonaqueous electrolytic solution, and it is sub- that nonaqueous electrolytic solution includes nonaqueous solvents, lithium hexafluoro phosphate, double fluorine sulfonamide
Lithium, difluoro-benzene and divinyl vinylene carbonate；Nonaqueous solvents is by ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate
Form, ethylene carbonate, dimethyl carbonate, the volume ratio of methyl ethyl carbonate are 1: 5: 4；Contain 0.9mol/L in nonaqueous electrolytic solution
Lithium hexafluoro phosphate and the double fluorine sulfonamide Asia lithiums of 0.1mol/L, the percentage of the weight of difluoro-benzene and the weight sum of nonaqueous solvents
Than for 2%, the percentage of the weight of divinyl vinylene carbonate and the weight sum of nonaqueous solvents is 2%.
Preferably, described positive electrode active materials are made comprising following raw materials according according to parts by weight：96 parts of positive electrode, gas
30 parts of 2 parts of phase grown carbon fiber, 2 parts of Kynoar and 1-METHYLPYRROLIDONE；The chemical formula of described positive electrode is：
Li4Ni4.7Co0.2Y0.1O8；X=0.1.
A kind of preparation technology of column lithium ion battery, the preparation technology include the preparation method of positive plate, negative plate
Preparation method and electrolyte preparation method,
The preparation method of positive plate comprises the following steps：
Step 1：After nickel salt aqueous solution, cobalt saline solution, the yttrium salt aqueous solution are well mixed, mixed solution is made；
Step 2：Mixed solution described in step 1 is placed in reaction vessel, adds the mixing of ammoniacal liquor and highly basic
Liquid, reaction solution is set to carry out coprecipitation reaction；The pH value of described reaction solution is 11~12；
Step 3：Sediment after terminating to coprecipitation reaction in step 2 carries out washing and drying, the sediment after drying
Middle addition lithium salts mixed at high speed in ball mill；200~1000rpm of rotating speed of described mixed at high speed, ratio of grinding media to material 3: 1~10
: 1,8~30h of Ball-milling Time；
Step 4：Mixture in step 3 in ball mill after mixed at high speed was through high-temperature roasting 24 hours, after standing room temperature
Through pulverizing and sieving, positive electrode is made；The temperature of described high-temperature roasting is 800~1100 DEG C, the screen cloth to pulverize and sieve
For 100~400 mesh；
Step 5：By the positive electrode described in step 4, vapor-grown carbon fibers, Kynoar and N- methylpyrroles
Alkanone is placed on be uniformly dispersed in planetary high speed dispersing device after, be spread evenly across on aluminium foil, after roll-in be made positive plate；
The thickness of described aluminium foil is 12 μm, and described positive plate thickness is 130 μm；
The preparation method of negative plate：By carbon negative pole material, vapor-grown carbon fibers, sodium carboxymethylcellulose, butadiene-styrene rubber
It is respectively put into after being uniformly dispersed in planetary high-speed dispersion equipment, is spread evenly across on the copper foil that thickness is 6 μm with deionized water,
The negative plate that thickness is 130 μm is obtained after roll-in；
The preparation method of electrolyte comprises the following steps：
Step 1：Ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate are mixed, and are made non-aqueous after being well mixed
Agent；
Step 2：Lithium hexafluoro phosphate and double fluorine sulfonamide Asias lithium are added into the nonaqueous solvents described in step 1, is made
Lithium salts nonaqueous solvents；
Step 3：Difluoro-benzene is sequentially added into the lithium salts nonaqueous solvents described in step 2 and divinyl carbonic acid is sub-
Vinyl acetate, you can.
Preferably, described nickel salt aqueous solution is selected from nickel sulfate solution, nickel nitrate aqueous solution, nickel chloride aqueous solution or vinegar
One of sour nickel aqueous solution；Cobalt saline solution is selected from cobalt sulfate solution, cobalt nitrate aqueous solution, cobalt chloride solution or cobalt acetate water
One of solution；The yttrium salt aqueous solution be selected from the yttrium sulfate aqueous solution, yttrium nitrate aqueous solution, the yttrium chloride aqueous solution or the acetic acid yttrium aqueous solution it
One；The mol ratio of the cobalt in nickel, cobalt saline solution in nickel salt aqueous solution and the yttrium in the yttrium salt aqueous solution is 5-3x: 2x: x, institute
The X stated is more than 0, and less than 0.5.
Preferably, one kind in potassium hydroxide solution, sodium hydroxide solution, lithium hydroxide solution of described highly basic or
It is several.
For the more detailed explanation present invention, further explaination is done to the present invention in conjunction with embodiment.Specific embodiment
It is as follows：
Embodiment one
A kind of column lithium ion battery, the column lithium ion battery include box hat, lithium-ion electric core, are respectively provided at lithium
Insulating trip and lower insulating trip, lithium-ion electric core include being sequentially stacked and wind on ion battery core upper and lower part positive plate, the
Electrolyte is provided with inside one barrier film, negative plate and the second barrier film, box hat,
The positive plate includes aluminium foil and is located at the positive electrode active materials of aluminium foil surface；Described positive electrode active materials include
Following raw materials according is made according to parts by weight：94 parts of positive electrode, 0.1 part of vapor-grown carbon fibers, 1 part of Kynoar and N- first
10 parts of base pyrrolidones；
The chemical formula of described positive electrode is：Li4Ni4.7Co0.2Y0.1O8, X=0.1；
The negative plate includes copper foil and is located at the negative active core-shell material of copper foil surface；Described negative active core-shell material includes
Following raw materials according is made according to parts by weight：95 parts of carbon negative pole material, 1 part of vapor-grown carbon fibers, sodium carboxymethylcellulose 1.5
50 parts of part, 2.5 parts of butadiene-styrene rubber and deionized water；Described carbon negative pole material is Delanium；
The electrolyte is nonaqueous electrolytic solution, and it is sub- that nonaqueous electrolytic solution includes nonaqueous solvents, lithium hexafluoro phosphate, double fluorine sulfonamide
Lithium, difluoro-benzene and divinyl vinylene carbonate；Nonaqueous solvents is by ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate
Form, ethylene carbonate, dimethyl carbonate, the volume ratio of methyl ethyl carbonate are 1: 5: 4；Contain 0.9mol/L in nonaqueous electrolytic solution
Lithium hexafluoro phosphate and the double fluorine sulfonamide Asia lithiums of 0.1mol/L, the percentage of the weight of difluoro-benzene and the weight sum of nonaqueous solvents
Than for 2%, the percentage of the weight of divinyl vinylene carbonate and the weight sum of nonaqueous solvents is 2%.
A kind of preparation technology of column lithium ion battery, the preparation technology include the preparation method of positive plate, negative plate
Preparation method and electrolyte preparation method,
The preparation method of positive plate comprises the following steps：
Step 1：After nickel salt aqueous solution, cobalt saline solution, the yttrium salt aqueous solution are well mixed, mixed solution is made；
Step 2：Mixed solution described in step 1 is placed in reaction vessel, adds the mixing of ammoniacal liquor and highly basic
Liquid, reaction solution is set to carry out coprecipitation reaction；The pH value of described reaction solution is 11~12；
Step 3：Sediment after terminating to coprecipitation reaction in step 2 carries out washing and drying, the sediment after drying
Middle addition lithium salts mixed at high speed in ball mill；200~1000rpm of rotating speed of described mixed at high speed, ratio of grinding media to material 3: 1, ball
Consume time 8h；
Step 4：Mixture in step 3 in ball mill after mixed at high speed was through high-temperature roasting 24 hours, after standing room temperature
Through pulverizing and sieving, positive electrode is made；The temperature of described high-temperature roasting is 800~11100 DEG C, the screen cloth to pulverize and sieve
For 100~400 mesh；
Step 5：By the positive electrode described in step 4, vapor-grown carbon fibers, Kynoar and N- methylpyrroles
Alkanone is placed on be uniformly dispersed in planetary high speed dispersing device after, be spread evenly across on aluminium foil, after roll-in be made positive plate；
The thickness of described aluminium foil is 12 μm, and described positive plate thickness is 130 μm；
The preparation method of negative plate：By carbon negative pole material, vapor-grown carbon fibers, sodium carboxymethylcellulose, butadiene-styrene rubber
It is respectively put into after being uniformly dispersed in planetary high-speed dispersion equipment, is spread evenly across on the copper foil that thickness is 6 μm with deionized water,
The negative plate that thickness is 130 μm is obtained after roll-in；
The preparation method of electrolyte comprises the following steps：
Step 1：Ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate are mixed, and are made non-aqueous after being well mixed
Agent；
Step 2：Lithium hexafluoro phosphate and double fluorine sulfonamide Asias lithium are added into the nonaqueous solvents described in step 1, is made
Lithium salts nonaqueous solvents；
Step 3：Difluoro-benzene is sequentially added into the lithium salts nonaqueous solvents described in step 2 and divinyl carbonic acid is sub-
Vinyl acetate, you can.
Preferably, described nickel salt aqueous solution is nickel sulfate solution；Cobalt saline solution is cobalt sulfate solution；Yttrium salt water
Solution is the aqueous solution of yttrium sulfate；Cobalt in nickel, cobalt saline solution in nickel salt aqueous solution rubs with the yttrium in the yttrium salt aqueous solution
You are than being 5-3x: 2x: x, described X=0.1.
Preferably, described highly basic is potassium hydroxide solution.
Embodiment two
A kind of column lithium ion battery, the column lithium ion battery include box hat, lithium-ion electric core, are respectively provided at lithium
Insulating trip and lower insulating trip, lithium-ion electric core include being sequentially stacked and wind on ion battery core upper and lower part positive plate, the
Electrolyte is provided with inside one barrier film, negative plate and the second barrier film, box hat,
The positive plate includes aluminium foil and is located at the positive electrode active materials of aluminium foil surface；Described positive electrode active materials include
Following raw materials according is made according to parts by weight：98 parts of positive electrode, 3 parts of vapor-grown carbon fibers, 3 parts of Kynoar and N- methyl
40 parts of pyrrolidones；
The chemical formula of described positive electrode is：Li4Ni3.8Co0.8Y0.4O8(0 ＜ X ＜ 0.5), X=0.4；
The negative plate includes copper foil and is located at the negative active core-shell material of copper foil surface；Described negative active core-shell material includes
Following raw materials according is made according to parts by weight：95 parts of carbon negative pole material, 1 part of vapor-grown carbon fibers, sodium carboxymethylcellulose 1.5
50 parts of part, 2.5 parts of butadiene-styrene rubber and deionized water；Described carbon negative pole material is native graphite；
The electrolyte is nonaqueous electrolytic solution, and it is sub- that nonaqueous electrolytic solution includes nonaqueous solvents, lithium hexafluoro phosphate, double fluorine sulfonamide
Lithium, difluoro-benzene and divinyl vinylene carbonate；Nonaqueous solvents is by ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate
Form, ethylene carbonate, dimethyl carbonate, the volume ratio of methyl ethyl carbonate are 1: 5: 4；Contain 0.9mol/L in nonaqueous electrolytic solution
Lithium hexafluoro phosphate and the double fluorine sulfonamide Asia lithiums of 0.1mol/L, the percentage of the weight of difluoro-benzene and the weight sum of nonaqueous solvents
Than for 2%, the percentage of the weight of divinyl vinylene carbonate and the weight sum of nonaqueous solvents is 2%.
A kind of preparation technology of column lithium ion battery, the preparation technology include the preparation method of positive plate, negative plate
Preparation method and electrolyte preparation method,
The preparation method of positive plate comprises the following steps：
Step 1：After nickel salt aqueous solution, cobalt saline solution, the yttrium salt aqueous solution are well mixed, mixed solution is made；
Step 2：Mixed solution described in step 1 is placed in reaction vessel, adds the mixing of ammoniacal liquor and highly basic
Liquid, reaction solution is set to carry out coprecipitation reaction；The pH value of described reaction solution is 11~12；
Step 3：Sediment after terminating to coprecipitation reaction in step 2 carries out washing and drying, the sediment after drying
Middle addition lithium salts mixed at high speed in ball mill；200~1000rpm of rotating speed of described mixed at high speed, ratio of grinding media to material 10: 1, ball
Consume time 30h；
Step 4：Mixture in step 3 in ball mill after mixed at high speed was through high-temperature roasting 24 hours, after standing room temperature
Through pulverizing and sieving, positive electrode is made；The temperature of described high-temperature roasting is 800~1100 DEG C, the screen cloth to pulverize and sieve
For 100~400 mesh；
Step 5：By the positive electrode described in step 4, vapor-grown carbon fibers, Kynoar and N- methylpyrroles
Alkanone is placed on be uniformly dispersed in planetary high speed dispersing device after, be spread evenly across on aluminium foil, after roll-in be made positive plate；
The thickness of described aluminium foil is 12 μm, and described positive plate thickness is 130 μm；
The preparation method of negative plate：By carbon negative pole material, vapor-grown carbon fibers, sodium carboxymethylcellulose, butadiene-styrene rubber
It is respectively put into after being uniformly dispersed in planetary high-speed dispersion equipment, is spread evenly across on the copper foil that thickness is 6 μm with deionized water,
The negative plate that thickness is 130 μm is obtained after roll-in；
The preparation method of electrolyte comprises the following steps：
Step 1：Ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate are mixed, and are made non-aqueous after being well mixed
Agent；
Step 2：Lithium hexafluoro phosphate and double fluorine sulfonamide Asias lithium are added into the nonaqueous solvents described in step 1, is made
Lithium salts nonaqueous solvents；
Step 3：Difluoro-benzene is sequentially added into the lithium salts nonaqueous solvents described in step 2 and divinyl carbonic acid is sub-
Vinyl acetate, you can.
Preferably, described nickel salt aqueous solution is nickel nitrate aqueous solution；Cobalt saline solution is cobalt nitrate aqueous solution；Yttrium salt water
Solution is yttrium nitrate aqueous solution；Mole of the cobalt and the yttrium in the yttrium salt aqueous solution in nickel, cobalt saline solution in nickel salt aqueous solution
Than for 5-3x: 2x: x, described X=0.4.
Preferably, described highly basic is sodium hydroxide solution.
Embodiment three
A kind of column lithium ion battery, the column lithium ion battery include box hat, lithium-ion electric core, are respectively provided at lithium
Insulating trip and lower insulating trip, lithium-ion electric core include being sequentially stacked and wind on ion battery core upper and lower part positive plate, the
Electrolyte is provided with inside one barrier film, negative plate and the second barrier film, box hat,
The positive plate includes aluminium foil and is located at the positive electrode active materials of aluminium foil surface；Described positive electrode active materials include
Following raw materials according is made according to parts by weight：96 parts of positive electrode, 1.55 parts of vapor-grown carbon fibers, 2 parts of Kynoar and N-
25 parts of methyl pyrrolidone；
The chemical formula of described positive electrode is：Li4Ni4.25Co0.5Y0.25O8, X=0.25；
The negative plate includes copper foil and is located at the negative active core-shell material of copper foil surface；Described negative active core-shell material includes
Following raw materials according is made according to parts by weight：95 parts of carbon negative pole material, 1 part of vapor-grown carbon fibers, sodium carboxymethylcellulose 1.5
50 parts of part, 2.5 parts of butadiene-styrene rubber and deionized water；Described carbon negative pole material is carbonaceous mesophase spherules；
The electrolyte is nonaqueous electrolytic solution, and it is sub- that nonaqueous electrolytic solution includes nonaqueous solvents, lithium hexafluoro phosphate, double fluorine sulfonamide
Lithium, difluoro-benzene and divinyl vinylene carbonate；Nonaqueous solvents is by ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate
Form, ethylene carbonate, dimethyl carbonate, the volume ratio of methyl ethyl carbonate are 1: 5: 4；Contain 0.9mol/L in nonaqueous electrolytic solution
Lithium hexafluoro phosphate and the double fluorine sulfonamide Asia lithiums of 0.1mol/L, the percentage of the weight of difluoro-benzene and the weight sum of nonaqueous solvents
Than for 2%, the percentage of the weight of divinyl vinylene carbonate and the weight sum of nonaqueous solvents is 2%.
A kind of preparation technology of column lithium ion battery, the preparation technology include the preparation method of positive plate, negative plate
Preparation method and electrolyte preparation method,
The preparation method of positive plate comprises the following steps：
Step 1：After nickel salt aqueous solution, cobalt saline solution, the yttrium salt aqueous solution are well mixed, mixed solution is made；
Step 2：Mixed solution described in step 1 is placed in reaction vessel, adds the mixing of ammoniacal liquor and highly basic
Liquid, reaction solution is set to carry out coprecipitation reaction；The pH value of described reaction solution is 11~12；
Step 3：Sediment after terminating to coprecipitation reaction in step 2 carries out washing and drying, the sediment after drying
Middle addition lithium salts mixed at high speed in ball mill；200~1000rpm of rotating speed of described mixed at high speed, ratio of grinding media to material 6.5: 1,
Ball-milling Time 19h；
Step 4：Mixture in step 3 in ball mill after mixed at high speed was through high-temperature roasting 24 hours, after standing room temperature
Through pulverizing and sieving, positive electrode is made；The temperature of described high-temperature roasting is 800~1100 DEG C, the screen cloth to pulverize and sieve
For 100~400 mesh；
Step 5：By the positive electrode described in step 4, vapor-grown carbon fibers, Kynoar and N- methylpyrroles
Alkanone is placed on be uniformly dispersed in planetary high speed dispersing device after, be spread evenly across on aluminium foil, after roll-in be made positive plate；
The thickness of described aluminium foil is 12 μm, and described positive plate thickness is 130 μm；
The preparation method of negative plate：By carbon negative pole material, vapor-grown carbon fibers, sodium carboxymethylcellulose, butadiene-styrene rubber
It is respectively put into after being uniformly dispersed in planetary high-speed dispersion equipment, is spread evenly across on the copper foil that thickness is 6 μm with deionized water,
The negative plate that thickness is 130 μm is obtained after roll-in；
The preparation method of electrolyte comprises the following steps：
Step 1：Ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate are mixed, and are made non-aqueous after being well mixed
Agent；
Step 2：Lithium hexafluoro phosphate and double fluorine sulfonamide Asias lithium are added into the nonaqueous solvents described in step 1, is made
Lithium salts nonaqueous solvents；
Step 3：Difluoro-benzene is sequentially added into the lithium salts nonaqueous solvents described in step 2 and divinyl carbonic acid is sub-
Vinyl acetate, you can.
Preferably, described nickel salt aqueous solution is nickel chloride aqueous solution；Cobalt saline solution is cobalt chloride solution；Yttrium salt water
Solution is the yttrium chloride aqueous solution；Mole of the cobalt and the yttrium in the yttrium salt aqueous solution in nickel, cobalt saline solution in nickel salt aqueous solution
Than for 5-3x: 2x: x, described X=0.25.
Preferably, described highly basic is lithium hydroxide solution.
Example IV
A kind of column lithium ion battery, the column lithium ion battery include box hat, lithium-ion electric core, are respectively provided at lithium
Insulating trip and lower insulating trip, lithium-ion electric core include being sequentially stacked and wind on ion battery core upper and lower part positive plate, the
Electrolyte is provided with inside one barrier film, negative plate and the second barrier film, box hat,
The positive plate includes aluminium foil and is located at the positive electrode active materials of aluminium foil surface；Described positive electrode active materials include
Following raw materials according is made according to parts by weight：95 parts of positive electrode, 2.5 parts of vapor-grown carbon fibers, 3 parts of Kynoar and N- first
18 parts of base pyrrolidones；
The chemical formula of described positive electrode is：Li4Ni3.53Co0.98Y0.49O8, X=0.49；
The negative plate includes copper foil and is located at the negative active core-shell material of copper foil surface；Described negative active core-shell material includes
Following raw materials according is made according to parts by weight：95 parts of carbon negative pole material, 1 part of vapor-grown carbon fibers, sodium carboxymethylcellulose 1.5
50 parts of part, 2.5 parts of butadiene-styrene rubber and deionized water；Described carbon negative pole material is petroleum coke；
The electrolyte is nonaqueous electrolytic solution, and it is sub- that nonaqueous electrolytic solution includes nonaqueous solvents, lithium hexafluoro phosphate, double fluorine sulfonamide
Lithium, difluoro-benzene and divinyl vinylene carbonate；Nonaqueous solvents is by ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate
Form, ethylene carbonate, dimethyl carbonate, the volume ratio of methyl ethyl carbonate are 1: 5: 4；Contain 0.9mol/L in nonaqueous electrolytic solution
Lithium hexafluoro phosphate and the double fluorine sulfonamide Asia lithiums of 0.1mol/L, the percentage of the weight of difluoro-benzene and the weight sum of nonaqueous solvents
Than for 2%, the percentage of the weight of divinyl vinylene carbonate and the weight sum of nonaqueous solvents is 2%.
A kind of preparation technology of column lithium ion battery, the preparation technology include the preparation method of positive plate, negative plate
Preparation method and electrolyte preparation method,
The preparation method of positive plate comprises the following steps：
Step 1：After nickel salt aqueous solution, cobalt saline solution, the yttrium salt aqueous solution are well mixed, mixed solution is made；
Step 2：Mixed solution described in step 1 is placed in reaction vessel, adds the mixing of ammoniacal liquor and highly basic
Liquid, reaction solution is set to carry out coprecipitation reaction；The pH value of described reaction solution is 11~12；
Step 3：Sediment after terminating to coprecipitation reaction in step 2 carries out washing and drying, the sediment after drying
Middle addition lithium salts mixed at high speed in ball mill；200~1000rpm of rotating speed of described mixed at high speed, ratio of grinding media to material 4: 1, ball
Consume time 28h；
Step 4：Mixture in step 3 in ball mill after mixed at high speed was through high-temperature roasting 24 hours, after standing room temperature
Through pulverizing and sieving, positive electrode is made；The temperature of described high-temperature roasting is 800~1100 DEG C, the screen cloth to pulverize and sieve
For 100~400 mesh；
Step 5：By the positive electrode described in step 4, vapor-grown carbon fibers, Kynoar and N- methylpyrroles
Alkanone is placed on be uniformly dispersed in planetary high speed dispersing device after, be spread evenly across on aluminium foil, after roll-in be made positive plate；
The thickness of described aluminium foil is 12 μm, and described positive plate thickness is 130 μm；
The preparation method of negative plate：By carbon negative pole material, vapor-grown carbon fibers, sodium carboxymethylcellulose, butadiene-styrene rubber
It is respectively put into after being uniformly dispersed in planetary high-speed dispersion equipment, is spread evenly across on the copper foil that thickness is 6 μm with deionized water,
The negative plate that thickness is 130 μm is obtained after roll-in；
The preparation method of electrolyte comprises the following steps：
Step 1：Ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate are mixed, and are made non-aqueous after being well mixed
Agent；
Step 2：Lithium hexafluoro phosphate and double fluorine sulfonamide Asias lithium are added into the nonaqueous solvents described in step 1, is made
Lithium salts nonaqueous solvents；
Step 3：Difluoro-benzene is sequentially added into the lithium salts nonaqueous solvents described in step 2 and divinyl carbonic acid is sub-
Vinyl acetate, you can.
Preferably, described nickel salt aqueous solution is nickel acetate aqueous solution；Cobalt saline solution is the cobalt acetate aqueous solution；Yttrium salt water
Solution is the acetic acid yttrium aqueous solution；Mole of the cobalt and the yttrium in the yttrium salt aqueous solution in nickel, cobalt saline solution in nickel salt aqueous solution
Than for 5-3x: 2x: x, described X=0.49.
Preferably, described highly basic is sodium hydroxide solution and lithium hydroxide solution.
Embodiment five
A kind of column lithium ion battery, the column lithium ion battery include box hat, lithium-ion electric core, are respectively provided at lithium
Insulating trip and lower insulating trip, lithium-ion electric core include being sequentially stacked and wind on ion battery core upper and lower part positive plate, the
Electrolyte is provided with inside one barrier film, negative plate and the second barrier film, box hat,
Described positive electrode active materials are made comprising following raw materials according according to parts by weight：96 parts of positive electrode, vapor phase growth
30 parts of 2 parts of Carbon fibe, 2 parts of Kynoar and 1-METHYLPYRROLIDONE；The chemical formula of described positive electrode is：
Li4Ni4.7Co0.2Y0.1O8；X=0.1；
The negative plate includes copper foil and is located at the negative active core-shell material of copper foil surface；Described negative active core-shell material includes
Following raw materials according is made according to parts by weight：95 parts of carbon negative pole material, 1 part of vapor-grown carbon fibers, sodium carboxymethylcellulose 1.5
50 parts of part, 2.5 parts of butadiene-styrene rubber and deionized water；Described carbon negative pole material is carbon fiber；
The electrolyte is nonaqueous electrolytic solution, and it is sub- that nonaqueous electrolytic solution includes nonaqueous solvents, lithium hexafluoro phosphate, double fluorine sulfonamide
Lithium, difluoro-benzene and divinyl vinylene carbonate；Nonaqueous solvents is by ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate
Form, ethylene carbonate, dimethyl carbonate, the volume ratio of methyl ethyl carbonate are 1: 5: 4；Contain 0.9mol/L in nonaqueous electrolytic solution
Lithium hexafluoro phosphate and the double fluorine sulfonamide Asia lithiums of 0.1mol/L, the percentage of the weight of difluoro-benzene and the weight sum of nonaqueous solvents
Than for 2%, the percentage of the weight of divinyl vinylene carbonate and the weight sum of nonaqueous solvents is 2%.
A kind of preparation technology of column lithium ion battery, the preparation technology include the preparation method of positive plate, negative plate
Preparation method and electrolyte preparation method,
The preparation method of positive plate comprises the following steps：
Step 1：After nickel salt aqueous solution, cobalt saline solution, the yttrium salt aqueous solution are well mixed, mixed solution is made；
Step 2：Mixed solution described in step 1 is placed in reaction vessel, adds the mixing of ammoniacal liquor and highly basic
Liquid, reaction solution is set to carry out coprecipitation reaction；The pH value of described reaction solution is 11~12；
Step 3：Sediment after terminating to coprecipitation reaction in step 2 carries out washing and drying, the sediment after drying
Middle addition lithium salts mixed at high speed in ball mill；200~1000rpm of rotating speed of described mixed at high speed, ratio of grinding media to material 9: 1, ball
Consume time 9h；
Step 4：Mixture in step 3 in ball mill after mixed at high speed was through high-temperature roasting 24 hours, after standing room temperature
Through pulverizing and sieving, positive electrode is made；The temperature of described high-temperature roasting is 800~1100 DEG C, the screen cloth to pulverize and sieve
For 100~400 mesh；
Step 5：By the positive electrode described in step 4, vapor-grown carbon fibers, Kynoar and N- methylpyrroles
Alkanone is placed on be uniformly dispersed in planetary high speed dispersing device after, be spread evenly across on aluminium foil, after roll-in be made positive plate；
The thickness of described aluminium foil is 12 μm, and described positive plate thickness is 130 μm；
The preparation method of negative plate：By carbon negative pole material, vapor-grown carbon fibers, sodium carboxymethylcellulose, butadiene-styrene rubber
It is respectively put into after being uniformly dispersed in planetary high-speed dispersion equipment, is spread evenly across on the copper foil that thickness is 6 μm with deionized water,
The negative plate that thickness is 130 μm is obtained after roll-in；
The preparation method of electrolyte comprises the following steps：
Step 1：Ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate are mixed, and are made non-aqueous after being well mixed
Agent；
Step 2：Lithium hexafluoro phosphate and double fluorine sulfonamide Asias lithium are added into the nonaqueous solvents described in step 1, is made
Lithium salts nonaqueous solvents；
Step 3：Difluoro-benzene is sequentially added into the lithium salts nonaqueous solvents described in step 2 and divinyl carbonic acid is sub-
Vinyl acetate, you can.
Preferably, described nickel salt aqueous solution is nickel chloride aqueous solution；Cobalt saline solution is cobalt chloride solution；Yttrium salt water
Solution is yttrium nitrate aqueous solution；Mole of the cobalt and the yttrium in the yttrium salt aqueous solution in nickel, cobalt saline solution in nickel salt aqueous solution
Than for 5-3x: 2x: x, described X=0.1.
Preferably, described highly basic is selected from potassium hydroxide solution, sodium hydroxide solution and lithium hydroxide solution.
Embodiment six
A kind of column lithium ion battery, the column lithium ion battery include box hat, lithium-ion electric core, are respectively provided at lithium
Insulating trip and lower insulating trip, lithium-ion electric core include being sequentially stacked and wind on ion battery core upper and lower part positive plate, the
Electrolyte is provided with inside one barrier film, negative plate and the second barrier film, box hat,
The positive plate includes aluminium foil and is located at the positive electrode active materials of aluminium foil surface；Described positive electrode active materials include
Following raw materials according is made according to parts by weight：97 parts of positive electrode, 2.3 parts of vapor-grown carbon fibers, 1 part of Kynoar and N- first
40 parts of base pyrrolidones；
The chemical formula of described positive electrode is：Li4Ni4.1Co0.6Y0.3O8, X=0.3；
The negative plate includes copper foil and is located at the negative active core-shell material of copper foil surface；Described negative active core-shell material includes
Following raw materials according is made according to parts by weight：95 parts of carbon negative pole material, 1 part of vapor-grown carbon fibers, sodium carboxymethylcellulose 1.5
50 parts of part, 2.5 parts of butadiene-styrene rubber and deionized water；Described carbon negative pole material is thermal decomposed resins；
The electrolyte is nonaqueous electrolytic solution, and it is sub- that nonaqueous electrolytic solution includes nonaqueous solvents, lithium hexafluoro phosphate, double fluorine sulfonamide
Lithium, difluoro-benzene and divinyl vinylene carbonate；Nonaqueous solvents is by ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate
Form, ethylene carbonate, dimethyl carbonate, the volume ratio of methyl ethyl carbonate are 1: 5: 4；Contain 0.9mol/L in nonaqueous electrolytic solution
Lithium hexafluoro phosphate and the double fluorine sulfonamide Asia lithiums of 0.1mol/L, the percentage of the weight of difluoro-benzene and the weight sum of nonaqueous solvents
Than for 2%, the percentage of the weight of divinyl vinylene carbonate and the weight sum of nonaqueous solvents is 2%.
A kind of preparation technology of column lithium ion battery, the preparation technology include the preparation method of positive plate, negative plate
Preparation method and electrolyte preparation method,
The preparation method of positive plate comprises the following steps：
Step 1：After nickel salt aqueous solution, cobalt saline solution, the yttrium salt aqueous solution are well mixed, mixed solution is made；
Step 2：Mixed solution described in step 1 is placed in reaction vessel, adds the mixing of ammoniacal liquor and highly basic
Liquid, reaction solution is set to carry out coprecipitation reaction；The pH value of described reaction solution is 11~12；
Step 3：Sediment after terminating to coprecipitation reaction in step 2 carries out washing and drying, the sediment after drying
Middle addition lithium salts mixed at high speed in ball mill；200~1000rpm of rotating speed of described mixed at high speed, ratio of grinding media to material 5: 1, ball
Consume time 22h；
Step 4：Mixture in step 3 in ball mill after mixed at high speed was through high-temperature roasting 24 hours, after standing room temperature
Through pulverizing and sieving, positive electrode is made；The temperature of described high-temperature roasting is 800~1100 DEG C, the screen cloth to pulverize and sieve
For 100~400 mesh；
Step 5：By the positive electrode described in step 4, vapor-grown carbon fibers, Kynoar and N- methylpyrroles
Alkanone is placed on be uniformly dispersed in planetary high speed dispersing device after, be spread evenly across on aluminium foil, after roll-in be made positive plate；
The thickness of described aluminium foil is 12 μm, and described positive plate thickness is 130 μm；
The preparation method of negative plate：By carbon negative pole material, vapor-grown carbon fibers, sodium carboxymethylcellulose, butadiene-styrene rubber
It is respectively put into after being uniformly dispersed in planetary high-speed dispersion equipment, is spread evenly across on the copper foil that thickness is 6 μm with deionized water,
The negative plate that thickness is 130 μm is obtained after roll-in；
The preparation method of electrolyte comprises the following steps：
Step 1：Ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate are mixed, and are made non-aqueous after being well mixed
Agent；
Step 2：Lithium hexafluoro phosphate and double fluorine sulfonamide Asias lithium are added into the nonaqueous solvents described in step 1, is made
Lithium salts nonaqueous solvents；
Step 3：Difluoro-benzene is sequentially added into the lithium salts nonaqueous solvents described in step 2 and divinyl carbonic acid is sub-
Vinyl acetate, you can.
Preferably, described nickel salt aqueous solution is selected from nickel sulfate solution, nickel nitrate aqueous solution, nickel chloride aqueous solution or vinegar
One of sour nickel aqueous solution；Cobalt saline solution is selected from cobalt sulfate solution, cobalt nitrate aqueous solution, cobalt chloride solution or cobalt acetate water
One of solution；The yttrium salt aqueous solution be selected from the yttrium sulfate aqueous solution, yttrium nitrate aqueous solution, the yttrium chloride aqueous solution or the acetic acid yttrium aqueous solution it
One；The mol ratio of the cobalt in nickel, cobalt saline solution in nickel salt aqueous solution and the yttrium in the yttrium salt aqueous solution is 5-3x: 2x: x, institute
The X=0.3 stated.
Preferably, described highly basic is sodium hydroxide solution.
Comparative example 1
Compared with Example 1, using without Y3+Positive electrode LiNi1/3Co1/3Mn1/3O2, other are used and embodiment 1
It is identical.
Comparative example 2
Compared with Example 1, using without Y3+Positive electrode LiNi1/3Co1/3Mn1/3O2, in addition, positive plate roll-in is thick
Spend for 120 μm, remaining is same as Example 1.
Method of testing：
Capacity：Standard atmospheric pressure, 25 DEG C ± 2 DEG C of environment temperature, under conditions of relative humidity is 45%~80%, with
0.2C5A electric currents charge, and when battery terminal voltage reaches charging limitation voltage 4.5V, constant-voltage charge are changed to, until charging current is small
In or equal to 0.01C5Stop charging after A, after shelving 10min, with 0.2C5A current discharges, until battery terminal voltage is 3.0V, and
Record the discharge capacity of battery.
Circulation：By above-mentioned charging/discharging thereof retest battery capacity 100 times, and calculate the 100th discharge capacity and the 1st
Secondary discharge capacity is worth ratio.
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 | Comparative example 2 | |
| X values | 0.1 | 0.2 | 0.3 | 0.4 | 0.1 | 0 | 0 |
| Capacity | 3090 | 3120 | 3150 | 3110 | 3089 | 2985 | 2920 |
| Circulation | 92% | 93% | 92.5% | 94% | 91% | 85% | 82% |
From above-mentioned test data embodiment 1, embodiment 2, embodiment 3, embodiment 4 as can be seen that originally compared with comparative example 1
Invention anode material discharging capacity is more than comparative example discharge capacity of the cell.
From embodiment 5 and the contrast of comparative example 2 as can be seen that 130 μm of positive electrode roll-in thickness drops to 120 μm, to battery
Capacity impact is little, and comparative example 2 and comparative example 1 contrast, and roll-in thickness equally is dropped into 120 μm, under battery capacity from 130 μm
Drop is obvious, illustrates that cathode material structure of the present invention is more stable.From loop-around data it is also seen that positive electrode cyclicity of the present invention
Comparative example can be better than, illustrate that the trielement synergistic effect in material crystals of nickel cobalt yttrium is better than nickel cobalt manganese.
Foregoing detailed description illustrates only for the feasibility embodiment of the present invention, and they are simultaneously not used to
Limit the scope of the invention, all equivalent implementations made without departing from skill spirit of the present invention, change and transformation all should
Within protection scope of the present invention.
Claims (5)
1. a kind of column lithium ion battery, the column lithium ion battery include box hat, lithium-ion electric core, be respectively provided at lithium from
Insulating trip and lower insulating trip, lithium-ion electric core include being sequentially stacked and wind on sub- battery core upper and lower part positive plate, first
Electrolyte is provided with inside barrier film, negative plate and the second barrier film, box hat, it is characterised in that：
The positive plate includes aluminium foil and is located at the positive electrode active materials of aluminium foil surface；Described positive electrode active materials include following
Raw material is made according to parts by weight：Positive electrode 94-98 parts, vapor-grown carbon fibers 0.1-3 parts, Kynoar 1-3 parts and
1-METHYLPYRROLIDONE 10-40 parts；
The chemical formula of described positive electrode is：Li4Ni5-3XCo2XYXO8(0 ＜ X ＜ 0.5)；
The negative plate includes copper foil and is located at the negative active core-shell material of copper foil surface；Described negative active core-shell material includes following
Raw material is made according to parts by weight：95 parts of carbon negative pole material, 1 part of vapor-grown carbon fibers, 1.5 parts of sodium carboxymethylcellulose, fourth
50 parts of 2.5 parts of benzene rubber and deionized water；Described carbon negative pole material is Delanium, native graphite, carbonaceous mesophase spherules, stone
One of oil coke, carbon fiber or thermal decomposed resins；
The electrolyte is nonaqueous electrolytic solution, nonaqueous electrolytic solution include nonaqueous solvents, lithium hexafluoro phosphate, double fluorine sulfonamide Asia lithiums,
Difluoro-benzene and divinyl vinylene carbonate；Nonaqueous solvents is by ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate structure
Into ethylene carbonate, dimethyl carbonate, the volume ratio of methyl ethyl carbonate are 1: 5: 4；Contain 0.9mol/L's in nonaqueous electrolytic solution
The percentage of lithium hexafluoro phosphate and the double fluorine sulfonamide Asia lithiums of 0.1mol/L, the weight of difluoro-benzene and the weight sum of nonaqueous solvents
For 2%, the percentage of the weight of divinyl vinylene carbonate and the weight sum of nonaqueous solvents is 2%.
A kind of 2. column lithium ion battery according to claim 1, it is characterised in that：Described positive electrode active materials bag
It is made containing following raw materials according according to parts by weight：96 parts of positive electrode, 2 parts of vapor-grown carbon fibers, 2 parts of Kynoar and N- first
30 parts of base pyrrolidones；The chemical formula of described positive electrode is：Li4Ni4.7Co0.2Y0.1O8；X=0.1.
A kind of 3. preparation technology of column lithium ion battery as claimed in claim 1, it is characterised in that：The preparation technology bag
The preparation method of the preparation method of positive plate, the preparation method of negative plate and electrolyte is included,
The preparation method of positive plate comprises the following steps：
Step 1：After nickel salt aqueous solution, cobalt saline solution, the yttrium salt aqueous solution are well mixed, mixed solution is made；
Step 2：Mixed solution described in step 1 is placed in reaction vessel, the mixed liquor of ammoniacal liquor and highly basic is added, makes
Reaction solution carries out coprecipitation reaction；The pH value of described reaction solution is 11~12；
Step 3：Sediment after terminating to coprecipitation reaction in step 2 carries out washing and drying, adds in the sediment after drying
Enter lithium salts mixed at high speed in ball mill；200~1000rpm of rotating speed of described mixed at high speed, ratio of grinding media to material 3: 1~10: 1,
8~30h of Ball-milling Time；
Step 4：Mixture in step 3 in ball mill after mixed at high speed is stood after room temperature through powder through high-temperature roasting 24 hours
Broken sieving, is made positive electrode；The temperature of described high-temperature roasting is 800~1100 DEG C, and the screen cloth to pulverize and sieve is 100
~400 mesh；
Step 5：By the positive electrode described in step 4, vapor-grown carbon fibers, Kynoar and 1-METHYLPYRROLIDONE
It is placed on after being uniformly dispersed in planetary high speed dispersing device, is spread evenly across on aluminium foil, positive plate is made after roll-in；It is described
Aluminium foil thickness be 12 μm, described positive plate thickness be 130 μm；
The preparation method of negative plate：By carbon negative pole material, vapor-grown carbon fibers, sodium carboxymethylcellulose, butadiene-styrene rubber and go
Ionized water is respectively put into be uniformly dispersed in planetary high-speed dispersion equipment after, it is on 6 μm of copper foil, through roller to be spread evenly across thickness
The negative plate that thickness is 130 μm is obtained after pressure；
The preparation method of electrolyte comprises the following steps：
Step 1：Ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate are mixed, and nonaqueous solvents is made after being well mixed；
Step 2：Lithium hexafluoro phosphate and double fluorine sulfonamide Asias lithium are added into the nonaqueous solvents described in step 1, lithium salts is made
Nonaqueous solvents；
Step 3：Difluoro-benzene and divinyl vinylene carbonate are sequentially added into the lithium salts nonaqueous solvents described in step 2
Ester, you can.
A kind of 4. preparation technology of column lithium ion battery according to claim 3, it is characterised in that：Described nickel salt
The aqueous solution is selected from one of nickel sulfate solution, nickel nitrate aqueous solution, nickel chloride aqueous solution or nickel acetate aqueous solution；Cobalt saline solution
Selected from one of cobalt sulfate solution, cobalt nitrate aqueous solution, cobalt chloride solution or cobalt acetate aqueous solution；The yttrium salt aqueous solution is selected from sulphur
One of the sour yttrium aqueous solution, yttrium nitrate aqueous solution, the yttrium chloride aqueous solution or acetic acid yttrium aqueous solution；Nickel, cobalt salt in nickel salt aqueous solution
The mol ratio of cobalt in the aqueous solution and the yttrium in the yttrium salt aqueous solution is 5-3x: 2x: x, and described X is more than 0, and less than 0.5.
A kind of 5. preparation technology of column lithium ion battery according to claim 3, it is characterised in that：Described highly basic
One or more in potassium hydroxide solution, sodium hydroxide solution, lithium hydroxide solution.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2019188207A1 (en) * | 2018-03-27 | 2019-10-03 | ダイキン工業株式会社 | Electrolyte solution, electrochemical device, lithium ion secondary battery, module and compound |
| WO2019188210A1 (en) * | 2018-03-27 | 2019-10-03 | ダイキン工業株式会社 | Electrolyte solution, electrochemical device, lithium ion secondary battery, and module |
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| JPWO2019188207A1 (en) * | 2018-03-27 | 2021-01-14 | ダイキン工業株式会社 | Electrolyte, electrochemical device, lithium ion secondary battery, module and compound |
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